Hybrid colored metallic pigment

ABSTRACT

A thin film structure including a reflector layer; and a hybrid layer including an organic colored material and at least one of an organic filler and an inorganic filler; wherein a concentration of the at least one of an organic filler or an inorganic filler is in a range of from about 3 wt. % to about 30 wt. %. A method of making a thin film structure is also disclosed.

RELATED APPLICATIONS

The present application is a continuation application of U.S. patentapplication Ser. No. 15/849,558, filed Dec. 20, 2017, which claimspriority to U.S. Provisional Application No. 62/437,357, filed on Dec.21, 2016, the entire disclosure of which is hereby incorporated byreference.

FIELD OF THE INVENTION

The present disclosure generally relates to thin film structures, suchas pigments including a reflector layer and a hybrid layer having anorganic colored material and at least one of an organic filler or aninorganic filler. Methods of making the thin film structure, such aspigments, are also disclosed.

BACKGROUND OF THE INVENTION

Colored metallic pigments in their simplest form are manufactured fromcolored metals. Flakes in these pigments have been coated with coloredtransparent or semi-transparent low refractive index material or highrefractive index material. The color effect may come from a combinationof reflection, absorption and interference of incident light.Interference colors in interference pigments have been created byformation on the surface of an aluminum flake of a Fabry-Perot structurehaving a transparent dielectric and semi-transparent metallic absorber.

Methods of fabrication of colored metallic pigments vary in theirnature. In one method, the color of flaked aluminum pigment was obtainedby formation of a layer of aluminum oxide on its surface by wetoxidation of suspended aluminum flakes with water wherein the color ofthe pigment was controlled by the thickness of oxide. In another method,aluminum flakes were coated by layers of metal oxides by one of numerouswet chemistry methods, such as a hydrolysis of organic metal estercompounds, or by formation of a metal oxide layer by subjecting one ormore precursors of one or more desired metal oxides and an acidiccatalyst to microwave radiation, or by fluidized bed CVD. Pigments havealso been colored by sol-gel precipitation of silicon dioxide fromtetraethyl silicate together with a dispersed colorant. Vacuumdeposition technology has been used for fabrication of colored metallicpigment based on the Fabry-Perot structure. For example, coloredpigments with saturated color were produced when a spacer layer was madefrom a material with high (n>2) index of refraction. Color-shiftinginterference pigments were fabricated when the dielectric layer had alow index of refraction (n<1.6).

SUMMARY OF THE INVENTION

In an aspect, there is disclosed a thin film structure including areflector layer; and a hybrid layer including an organic coloredmaterial and at least one of an organic filler or an inorganic filler;wherein a concentration of the at least one of an organic filler or aninorganic filler is in a range of from about 3 wt. % to about 30 wt. %.

In another aspect, there is disclosed a method of making a thin filmstructure comprising providing a substrate with a release layer,depositing a first hybrid layer on the release layer by vacuumdeposition, depositing a reflector layer on the first hybrid layer, anddepositing a second first hybrid layer on the reflector layer to form athin film structure; wherein the first and second hybrid layer comprisesan organic colored material and at least one of an organic filler or aninorganic filler; and wherein a concentration of the at least oneorganic filler and an inorganic filler is in a range of from about 3 wt.% to about 30 wt. %.

Additional features and advantages of various embodiments will be setforth, in part, in the description that follows, and will, in part, beapparent from the description, or may be learned by the practice ofvarious embodiments. The objectives and other advantages of variousembodiments will be realized and attained by means of the elements andcombinations particularly pointed out in the description herein.

BRIEF DESCRIPTION OF THE DRAWINGS

The present disclosure in its several aspects and embodiments can bemore fully understood from the detailed description and the accompanyingdrawings, wherein:

FIG. 1 is a cross-sectional view of a thin film structure, according toan example of the present disclosure;

FIG. 2A is a cross-sectional view of a thin film structure prior tobeing released from a substrate having a release layer, according to anexample of the present disclosure;

FIG. 2B is a cross-sectional view of a thin film structure prior tobeing released from a substrate, according to an example of the presentdisclosure;

FIG. 3 is a graph of reflectance of a thin film structure, according toan example of the present disclosure;

FIG. 4 is a L*a*b* color space of a thin film structure, according to anexample of the present disclosure;

FIG. 5 is a graph of reflectance of a thin film structure, according toanother example of the present disclosure; and

FIG. 6 is a L*a*b* color space of a thin film structure, according toanother example of the present disclosure.

Throughout this specification and figures like reference numbersidentify like elements.

DETAILED DESCRIPTION OF THE INVENTION

It is to be understood that both the foregoing general description andthe following detailed description are exemplary and explanatory only,and are intended to provide an explanation of various embodiments of thepresent teachings.

Referring to FIGS. 1 and 2 , in their broad and varied embodiments,disclosed herein is a thin film structure 5 comprising a reflector layer1 and a hybrid layer 2A, 2B. The hybrid layer 2A, 2B can comprise anorganic colored material and at least one of an organic filler or aninorganic filler.

The total thickness of the thin film structure 5 can be less than 10microns, such as for example from less than about 5 microns. In anaspect, the total thickness of the thin film structure 5 can range fromabout 0.01 micron to about 10 micron, such as, from about 100 nm toabout 5000 nm, for example from about 100 nm to about 4000 nm.

For each example shown in FIGS. 1-2 , the materials for the reflectorlayer 1 can include any material that can render the reflector layer 1opaque. In an aspect, the material may be a metal and/or metal alloy. Inone example, the materials for the reflector layer 1 can include anymaterials that have reflective characteristics. An example of areflective material can be aluminum, which has good reflectancecharacteristics, is inexpensive, and easy to form into or deposit as athin layer. However, other reflective materials can also be used inplace of aluminum. For example, aluminum, zinc, steel, copper, silver,gold, platinum, palladium, nickel, cobalt, niobium, chromium, tin, andcombinations or alloys of these or other metals can be used asreflective materials, such as bronze, brass, and stainless steel. In anaspect, the material for the reflector layer 1 can be a white or lightcolored metal. Other useful reflective materials include, but are notlimited to, the transition and lanthanide metals and combinationsthereof.

The thickness of reflector layer 1 can range from about 40 nm to about150 nm, although this range should not be taken as restrictive. Forexample, the lower limit of 40 nm can be selected for a material such asaluminum so that the aluminum is of a minimum optical density of about0.5 at a wavelength of about 550 nm. Other reflector materials canjustify higher or lower minimum thicknesses in order to obtain asufficient optical density or achieve the desired effect. The upperlimit of about 150 nm can also be higher or lower depending on thedesired effect and the materials used.

The reflector layer 1 can be microstructured so as to provide adiffractive property of light. In an aspect, the reflector layer 1 canmade of any material and in any thickness so long as the reflector layer1 is opaque.

In one aspect, the thickness of the reflector layer 1 can range fromabout 10 nm to about 160 nm for example, from about 15 nm to about 150nm, from about 20 nm to about 140 nm, from about 25 nm to about 130 nm,from about 30 nm to about 120 nm, from about 40 nm to about 110 nm, orfrom about 50 nm to about 100 nm, such as from about 60 nm to about 90nm or from about 70 nm to about 80 nm.

The hybrid layer 2 for use in the thin film structure 5 can include anorganic colored material and at least one of an organic filler or aninorganic filler. The hybrid layer 2 can be more than one layer such asa first hybrid layer 2A, a second hybrid layer 2B, a third hybrid layer2C (not shown in the figures), etc. In an aspect, a hybrid layer 2 canbe present on opposite sides of the reflector layer 1. In anotheraspect, more than one hybrid layer 2 can be present on each side of thereflector layer 1. For example, one side of a reflector layer 1 caninclude up to three (3) hybrid layers 2A, 2B, 2C and a second side of areflector layer 1 can include up to three (3) hybrid layers, which canbe the same as the hybrid layers on the first side of reflector layer 1,or they can be different hybrid layers, such as hybrid layers 2D, 2E,2F.

Each of the hybrid layer 2 present in the thin film structure 5 can bethe same or different from one another. In an aspect, a first hybridlayer 2A can be the same composition as a second hybrid layer 2B. Inanother aspect, a first hybrid layer 2A can have the same thickness as asecond hybrid layer 2B. Alternatively, each hybrid layer 2 can bedifferent. A first hybrid layer 2A can be a different composition as asecond hybrid layer 2B. A first hybrid layer 2A can have a differentthickness as a second hybrid layer 2B. Each layer may vary, e.g., samecomposition, different thickness or different composition and samethickness.

The composition of the hybrid layer 2 can be selected to achieve acertain color or hue. In particular, by selecting a different organiccolored material present in each hybrid layer 2, then the combinedlayers can achieve a certain color or hue. For example, a first hybridlayer 2A can comprise an organic colored material that is yellow. Asecond hybrid layer 2B, present on top of the first hybrid layer 2A, cancomprise an organic colored material that is blue. The resultant coloror hue achieved can therefore be green. Similar combinations of organiccolored materials in various hybrid layers may result in other colorcombinations, such as a yellow hybrid layer 2A on a red hybrid layer 2Bcan result in an overall orange color or hue.

Alternatively, the thin film structure 5 can have a single hybrid layer2 on each side of the reflector layer 1, such as a green hybrid layer oran orange hybrid layer. The thin film structure 5 can include a redhybrid layer 2A on a first side of the reflector layer 1 and a bluehybrid layer 2B on a second side of the reflector layer 1.

The hybrid layer 2 can have a thickness of from about 10 nm to about5000 nm, such as from about 20 nm to about 4500 nm, for example fromabout 30 nm to about 4000 nm. In an aspect, the hybrid layer 2 is lessthan about 300 nm so that light is not scattered.

The organic colored material can be present in the hybrid layer 2 in anamount less than about 100% by weight relative to the total weight ofthe hybrid layer 2. It is expected that if there is 100% by weight oforganic colored material present in the hybrid layer 2, then the hybridlayer 2 can delaminate from the reflector layer 1.

The organic colored material can comprise any colored material, such asorganic pigments. Non-limiting organic pigments include, for exampleperylene, perinone, quinacridone, quinacridonequinone, anthrapyrimidine,anthraquinone, anthanthrone, benzimidazolone, disazo condensation, azo,azomethine, quinophthalone, indanthrone, phthalocyanine,triarylcarbonium, dioxazine, aminoanthraquinone, isoindolinediketopyrrolopyrrole, thioindigo, thiazineindigo, isoindoline,isoindolinone, pyranthrone, isoviolanthrone, or a mixture thereof.

Additional non-limiting examples of organic pigments for use as anorganic colored material include for example C.I. Pigment Red 123 (C.I.No. 71 145), C.I. Pigment Red 149 (C.I. No. 71 137), C.I. Pigment Red178 (C.I. No. 71 155), C.I. Pigment Red 179 (C.I. No. 71 130), C.I.Pigment Red 190 (C.I. 71 140), C.I. Pigment Red 224 (C.I. No. 71 127),C.I. Pigment Violet 29 (C.I. No. 71 129), C.I. Pigment Orange 43 (C.I.No. 71 105), C.I. Pigment Red 194 (C.I. No. 71 100), C.I. Pigment Violet19 (C.I. No. 73 900), C.I. Pigment Red 122 (C.I. No. 73 915), C.I.Pigment Red 192, C.I. Pigment Red 202 (C.I. No. 73 907), C.I. PigmentRed 207, C.I. Pigment Red 209 (C.I. No. 73 905), C.I. Pigment Red 206(C.I. No. 73 900/73 920), C.I. Pigment Orange 48 (C.I. No. 73 900/73920), C.I. Pigment Orange 49 (C.I. No. 73 900/73 920), C.I. PigmentOrange 42, C.I. Pigment Yellow 147, C.I. Pigment Red 168 (C.I. No. 59300), C.I. Pigment Yellow 120 (C.I. No. 11 783), C.I. Pigment Yellow 151(C.I. No. 13 980), C.I. Pigment Brown 25 (C.I. No. 12 510), C.I. PigmentViolet 32 (C.I. No. 12 517), C.I. Pigment Orange 64; C.I. Pigment Brown23 (C.I. No. 20 060), C.I. Pigment Red 166 (C.I. No. 20 730), C.I.Pigment Red 170 (C.I. No. 12 475), C.I. Pigment Orange 38 (C.I. No. 12367), C.I. Pigment Red 188 (C.I. No. 12 467), C.I. Pigment Red 187 (C.I.No. 12 486), C.I. Pigment Orange 34 (C.I. No. 21 115), C.I. PigmentOrange 13 (C.I. No. 21 110), C.I. Pigment Red 9 (C.I. No. 12 460), C.I.Pigment Red 2 (C.I. No. 12 310), C.I. Pigment Red 112 (C.I. No. 12 370),C.I. Pigment Red 7 (C.I. No. 12 420), C.I. Pigment Red 210 (C.I. No. 12477), C.I. Pigment Red 12 (C.I. No. 12 385), C.I. Pigment Blue 60 (C.I.No. 69 800), C.I. Pigment Green 7 (C.I. No. 74 260), C.I. Pigment Green36 (C.I. No. 74 265); C.I. Pigment Blue 15:1, 15:2, 15:3, 15:4, 15:6 and15 (C.I. No. 74 160); C.I. Pigment Blue 56 (C.I. No. 42 800), C.I.Pigment Blue 61 (C.I. No. 42 765:1), C.I. Pigment Violet 23 (C.I. No. 51319), C.I. Pigment Violet 37 (C.I. No. 51 345), C.I. Pigment Red 177(C.I. No. 65 300), C.I. Pigment Red 254 (C.I. No. 56 110), C.I. PigmentRed 255 (C.I. No. 56 1050), C.I. Pigment Red 264, C.I. Pigment Red 270,C.I. Pigment Red 272 (C.I. No. 56 1150), C.I. Pigment Red 71, C.I.Pigment Orange 73, C.I. Pigment Red 88 (C.I. No. 73 312), C.I. PigmentYellow 175 (C.I. No. 11 784), C.I. Pigment Yellow 154 (C.I. No. 11 781),C.I. Pigment Yellow 83 (C.I. No. 21 108), C.I. Pigment Yellow 180 (C.I.No. 21 290), C.I. Pigment Yellow 181 (C.I. No. 11 777), C.I. PigmentYellow 74 (C.I. No. 11 741), C.I. Pigment Yellow 213, C.I. PigmentOrange 36 (C.I. No. 11 780), C.I. Pigment Orange 62 (C.I. No. 11 775),C.I. Pigment Orange 72, C.I. Pigment Red 48:2/3/4 (C.I. No. 15865:2/3/4), C.I. Pigment Red 53:1 (C.I. No. 15 585:1), C.I. Pigment Red208 (C.I. No. 12 514), C.I. Pigment Red 185 (C.I. No. 12 516), C.I.Pigment Red 247 (C.I. No. 15 915).

The hybrid layer 2 can include at least one of organic filler orinorganic filler. The at least one organic filler or inorganic fillercan be present in the hybrid layer 2 in an amount ranging from about 3wt. % to about 30 wt. %, for example from about 3 wt. % to about 30 wt.% relative to the total weight of the hybrid layer 2. The amount of theat least one organic filler or inorganic filler can vary along agradient to achieve a coloration of concentration colors that provide adesirable color to the thin film structure. In an aspect, the at leastone of organic filler or inorganic filler can be present in the hybridlayer 2 in varying amounts or concentrations, such as along a length ofthe hybrid layer 2. For example, a concentration can taper along alength of the hybrid layer so that a first end of the hybrid layer canhave a higher concentration of, for example, an organic filler, and thesecond end of the hybrid layer can have a lower concentration of, forexample, the organic filler. Additionally, the first end of the hybridlayer can have a low concentration of, for example, an inorganic filler,and the second end of the hybrid layer can have a high concentration of,for example, the inorganic filler. This aspect can occur if the organicfiller or inorganic filler are deposited downstream one from the other.

In another aspect, the at least one organic filler or inorganic fillercan be uniformly dispersed in the hybrid layer 2. For example, the atleast one organic filler or inorganic filler can be pre-mixed andtherefore co-deposited with the organic colored material.

In yet another aspect, the at least one organic filler or inorganicfiller can be present in the hybrid layer 2 in an amount to improveadhesion. For example, a filler exhibiting poor adhesion characteristicscan be deposited after a filler exhibiting good adhesion has beendeposited. In this manner, the filler having good adhesion can be usedto more increase the adhesion of the filler having poor adhesion.

The organic filler or inorganic filler for use in the hybrid layer 2 canbe made from any materials. Non-limiting examples of suitable materialsinclude magnesium fluoride, silicon monoxide, silicon dioxide, aluminumoxide, aluminum fluoride, titanium dioxide, aluminum nitride, boronnitride, boron carbide, tungsten oxide, cerium fluoride, lanthanumfluoride, neodymium fluoride, samarium fluoride, barium fluoride,calcium fluoride, lithium fluoride, tungsten carbide, titanium carbide,titanium nitride, silicon nitride, zinc sulfide, glass flakes,diamond-like carbon, and combinations thereof.

The organic filler or inorganic filler can be made from materials havinga refractive index ranging from about 1.3 to about 2.3. In an aspect,the organic filler or inorganic filler can be a material having a lowrefractive index of less than about 1.65. In another aspect, the organicfiller or inorganic filler can be a material having a high refractiveindex of greater than about 2.2.

A method of making the thin film structure 5 can include providing asubstrate 4 with a release layer 3. The substrate 4 can be made of anymaterial. For example, a 1 mil polyester can be used as the substrate 4;however, other organic webs and other thicknesses can be used. Organicwebs can include polyethylene terephthalate, polyethylene, orientedpolypropylene, polycarbonate, polyvinylbutyral, polyhexadiene, andpolyimide. Alternatively, webs that do not require transparency can beused. The thickness of the substrate 4 can range from about 0.5 mil toabout 5 mil.

The method can include depositing a first hybrid layer 2 a onto asubstrate 4, as shown in FIG. 2B. The substrate 4 can include a releaselayer 3, as shown in FIG. 2A. In an aspect, the organic colored materialcan be co-deposited with at least one of the organic filler or theinorganic filler to deposit the first hybrid layer. The vacuumdeposition can be any known vacuum deposition technique, such asphysical vapor deposition, chemical vapor deposition, fluidized bedchemical vapor deposition, and the like. A reflector layer 1 can then bedeposited on the first hybrid layer 2A using any deposition techniquethat would not encapsulate the reflector layer 1. For example, thereflector layer 1 can be deposited by vacuum deposition. A second hybridlayer 2B can then be deposited onto the reflector layer 1 to form a thinfilm structure 5. The second hybrid layer 2B can be deposited using avacuum deposition technique.

The entire structure, i.e., the thin film structure 5 on the releaselayer 3 of the substrate 4, can then be immersed into a solvent, such asan organic solvent. The organic solvent can be anycarbon-compound-containing solvent, such as amides, sulfones,sulfolenes, selenones, and saturated alcohols. Non-limiting organicsolvents include methylene chloride, ethyl acetate, dimethyl sulfoxide,tetrahydrofuran, dimethylformamide, ethanol, sulfolane(tetrahydrothiopene-1,1-dioxide), 3-methylsulfolane, n-propyl sulfone,n-butyl sulfone, sulfolene (2,5-dihydrothiopene-1,1-dioxide),3-methylsulfolene, amides such as 1-(2-hydroxyethyl)-2-pyrrolidinone(HEP), dimethylpiperidone (DMPD), N-methyl pyrrolidinone (NMP), anddimethylacetamide (DMAc), dimethylformamide (DMF), propanol, butanol,hexanol, ethylene glycol, propylene glycol, glycerol, andhexafluoroisopropanol. The organic solvent can dissolve the releaselayer effectively separating the thin film structure 5 from thesubstrate 4.

The released thin film structure 5 can be filtered and sized usingstandard sizing techniques, such as mechanical grinding, for example byball milling, etc. The thin film structure 5 can be sized to achieve anaverage particle size ranging from about 5 to about 100 microns, forexample from about 7 to about 50 microns, a further example from about 9to about 40 microns, and as a further example from about 10 to about 20microns.

Thin film structure can have additional layers, such as a protectantlayer, a passivation layer, a dielectric layer.

The thin film structure 5 can be a pigment. The pigment can also includea liquid medium.

The thin film structure 5 can be used with light detection and radar(LIDAR) technology.

EXAMPLES Example 1

Magnesium fluoride and3,6-Bis(4-chlorophenyl)-2,5-dihydropyrrolo[3,4-c]pyrolle-1,4-dione(Pigment Red 254, CAS Number 84632-65-5) were simultaneously evaporatedin vacuum and deposited as a first hybrid layer 2B onto a release layer3 of a polyester substrate 4 until the thickness of the first hybridlayer 2B came to about 300 nm, as shown in FIG. 2 . The process wasstopped at this point and an 80 nm thick layer of reflector layer(copper) 1 was deposited on top of the first hybrid layer 2B. A secondhybrid layer 2A was deposited on the top of the reflector layer (copper)1. The polyester substrate 4 was coated with a solvent-sensitive releaselayer 3. The first hybrid layer 2B was coated on a top side of therelease layer 3. The reflector layer 1 was deposited on the top of therelease layer 3 and followed by a second hybrid layer 2A. The entirestructure was immersed in an organic solvent after completion of vacuumdeposition. The release layer 3 was dissolved and the three-layer thinfilm structure 5 was filtered and mechanically ground until the averagesize of the platelets was in the range of from about 10 to about 20microns. The total thickness of the thin film structure 5 was 670 nm.The magnesium fluoride (MgF₂) concentration in the hybrid layer 2A, 2Bwas about 26.5 wt. %. Reflectance of the thin film structure 5 isillustrated in FIG. 3 . The color of the pigment was red. The colorvalue of the pigment was illustrated in the L*a*b* color space in FIG. 4.

Example 2

Quinacridone violet (Pigment Violet 19, CAS Number: 1047-16-1) wasco-deposited with MgF₂ as a hybrid layer 2A, 2B in the structure similarto the one in FIG. 2 with aluminum as the reflector layer 1. The totalthickness of the thin film structure 5 was 721 nm with a MgF₂concentration of 16 wt. %. Reflectance of the thin film structure 5 isillustrated in FIG. 5 . The color of the pigment was violet. The colorvalue of the pigment was illustrated in the L*a*b* color space in FIG. 6.

From the foregoing description, those skilled in the art can appreciatethat the present teachings can be implemented in a variety of forms.Therefore, while these teachings have been described in connection withparticular embodiments and examples thereof, the true scope of thepresent teachings should not be so limited. Various changes andmodifications may be made without departing from the scope of theteachings herein.

This scope disclosure is to be broadly construed. It is intended thatthis disclosure disclose equivalents, means, systems and methods toachieve the devices, activities and mechanical actions disclosed herein.For each device, article, method, mean, mechanical element or mechanismdisclosed, it is intended that this disclosure also encompass in itsdisclosure and teaches equivalents, means, systems and methods forpracticing the many aspects, mechanisms and devices disclosed herein.Additionally, this disclosure regards a coating and its many aspects,features and elements. Such a device can be dynamic in its use andoperation, this disclosure is intended to encompass the equivalents,means, systems and methods of the use of the device and/or article ofmanufacture and its many aspects consistent with the description andspirit of the operations and functions disclosed herein. The claims ofthis application are likewise to be broadly construed.

The description of the inventions herein in their many embodiments ismerely exemplary in nature and, thus, variations that do not depart fromthe gist of the invention are intended to be within the scope of theinvention. Such variations are not to be regarded as a departure fromthe spirit and scope of the invention.

We claim:
 1. A thin film structure, comprising: a microstructuredreflector layer laving a first side and a second side; wherein the firstside includes two or three hybrid layers, and wherein the second sideincludes up to three hybrid layers, hybrid layer comprises an organiccolored material and at least one filler chosen from an organic fillerand an inorganic filler, wherein the at least one filler is present inthe hybrid layer in an amount ranging from about 3 wt. % to about 30 wt.% relative to the total weight of the hybrid layer.
 2. The thin filmstructure of claim 1, wherein the reflector layer is opaque.
 3. The thinfilm structure of claim 1, wherein the first side has three hybridlayers.
 4. The thin film structure of claim 1, wherein the first sidehas two hybrid layers.
 5. The thin film structure of claim 1, whereinthe second side has three hybrid layers.
 6. The thin film structure ofclaim 1, wherein the second side has two hybrid layers.
 7. The thin filmstructure of claim 4, wherein the two hybrid layers include differentorganic colored materials in each hybrid layer.
 8. The thin filmstructure of claim 3, wherein the three hybrid layers include differentorganic colored materials in each hybrid layer.
 9. The thin filmstructure of claim 1, wherein the at least one organic filler orinorganic filler is uniformly dispersed in the hybrid layer.
 10. Thethin film structure of claim 1, further comprising a protectant layer.11. The thin film structure of claim 1, further comprising a passivationlayer.
 12. The thin film structure of claim 1, further comprising adielectric, layer.
 13. The thin film structure of claim 1, wherein thereflector layer is copper, and the hybrid layer includes magnesiumfluoride and 3,6-Bis(4-chlorophenyl2,5-dihydropyrrolo[3,4-c]pyrolle-1,4-dione.
 14. The thin film structureof claim 1, wherein the reflector layer is aluminum, and the hybridlayer includes magnesium fluoride and quinacridone.
 15. A thin filmstructure, comprising: a microstructured reflector layer having a firstside and a second side; wherein the first side includes up to threehybrid layers, and wherein the second side includes up to three hybridlayers, a hybrid layer comprises an organic colored material and atleast one filler chosen from an organic filler and an inorganic filler,wherein the at least one filler is present in the hybrid layer in anamount ranging from about 3 wt. % to about 30 wt. % relative to thetotal weight of the hybrid layer, wherein an amount of the at least oneorganic filler or inorganic filler varies along a gradient along alength of the hybrid layer.
 16. The thin film structure of claim 1,wherein a first end of the hybrid layer has a higher concentration ofthe at least one organic filler or inorganic filler as compared to asecond end of the hybrid layer.
 17. A method of making a thin filmstructure, comprising: a. co-depositing, on a reflector layer, anorganic colored material and at least one filler chosen from an organicfiller and an inorganic filler to form a hybrid layer, and b.mechanically grinding the thin film structure to an average plateletsize of 10 to 20 microns, wherein the at least one filler is present inthe hybrid layer in an amount ranging from about 3 wt. % to about 30 wt.% relative to the total weight of the hybrid layer.
 18. A method ofmaking a thin film structure, comprising: providing a substrate with arelease layer; co-depositing, on the substrate with release layer, anorganic colored material and at least one filler chosen from an organicfiller and an inorganic filler to form a first hybrid layer;co-depositing, on a reflector layer, an organic colored material and atleast one filler chosen from an organic filler and an inorganic fillerto form a second hybrid layer, wherein the at least one filler ispresent in the hybrid layer in an amount ranging from about 3 wt. % toabout 30 wt. % relative to the total weight of the hybrid layer.
 19. Themethod of claim 18, wherein the reflector layer is deposited on thefirst hybrid layer.